US4829109A - Polymeric compositions suitable for use as bitumen modifiers and bituminous compositions so modified - Google Patents
Polymeric compositions suitable for use as bitumen modifiers and bituminous compositions so modified Download PDFInfo
- Publication number
- US4829109A US4829109A US06/860,917 US86091786A US4829109A US 4829109 A US4829109 A US 4829109A US 86091786 A US86091786 A US 86091786A US 4829109 A US4829109 A US 4829109A
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- ethylene
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- bitumen
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
Definitions
- the present invention relates to polymeric compositions suitable to be used as agents for bitumen modification, as well as to the so modified bituminous compositions.
- bituminous compositions as sheaths, in the water-proofing of civil and industrial buildings.
- Such compositions are prevailingly constituted by bitumen of the distillate type, and generally contain modifier agents which improve their physical-mechanical characteristics--in particular, their resistance to high-temperature penetration and their low-temperature flexibility.
- Such agents are generally constituted by amorphous polypropylene (in amount of from 20 to 30% by weight), possibly in combination with amorphous or low-crystallinity olefinic copolymers having low molecular weight.
- polypropylene prevailingly constituted by isotactic macromolecules having M.I. greater than 1 and preferably comprised within the range of from 5 to 15;
- component (c) 0-70% of substantially amorphous polypropylene, possibly in mixture with amorphous copolymers of ethylene with propylene, such component (c) having a total combined ethylene content lower than 60% by weight, and intrinsic viscosity (in tetralin at 135° C.) lower than 2 dl/g and preferably comprised with the range of from 0.1 to 1;
- ethylene/vinyl acetate (EVA) copolymer containing from 60 to 95% by weight of ethylene, having a value of M.I. higher than 0.1, and preferably comprised within the range of from 0.5 to 200;
- EVA ethylene/vinyl acetate
- component (c) is equal to zero
- the polymeric compositions as defined above can be used as modifiers for bitumen by mixing with this latter.
- Inert mineral fillers such as silica, kaolin, micas, calcium carbonate etc., can be present in the mixture of bitumen with such modifiers, in amounts of up to 20% by weight as referred to the total mixture weight.
- the above said modifier compositions can be used in amounts comprised within the range of from 10 to 30%, but preferably of from 12 to 25% by weight, as referred to the total weight of the mixture with bitumen and possible fillers.
- An object of the present invention is hence constituted by the polymeric compositions suitable to be used as additives in bituminous compositions, comprising a mixture of components from (a) to (e) in the above indicated proportions.
- a further object of the present invention is constituted by the bituminous compositions comprising from 10% to 30% by weight of the polymeric composition as defined above.
- the polymeric compositions of the present invention can be prepared in form of granules by mixing their components either in extruder, or in Banbury or roller mixer, at such temperatures as to allow such components to be intimately mixed in the mixture, and subsequent granulation.
- bituminous compositions which are the further object of the present invention can be prepared by high-temperature mixing bitumen (possibly with the addition of inert mineral fillers such as for example kaolin, CaCO 3 , SiO 2 , mica) either with 10-30% by weight, with reference to the total weight of the bituminous composition, of the polymeric composition as defined above, or with the individual components thereof, separately added in an altogether equivalent amount.
- bitumen possibly with the addition of inert mineral fillers such as for example kaolin, CaCO 3 , SiO 2 , mica
- the ethylene/propylene copolymers [component (a)] can be prepared according to known methods. Among such copolymers those obtained by using high-yield catalysts, on the basis of titanium comounds, such as, e.g., those disclosed in U.S. Pat. No. 4,013,823 to the Applicant's name, are preferred.
- a bituminous composition is prepared by mixing, in a stainless-steel cylindrical container, at the temperature of 200° C., for 60 minutes and by blade stirrer (500 rpm):
- bitumen type 180/200 65 parts by weight
- bituminous composition which is constituted by:
- bitumen type 180/200 76 parts by weight
- the so-obtained blend is extruded and granulated.
- bituminous composition is prepared as in Comparative Example 1, with the difference that bitumen of type 80/100 is used.
- bituminous composition by operating as in Example 1.
- ML 1+4 Mooney viscosity
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(1) Polymeric compositions, suitable for use as bitumen modifiers, comprising, by weight:
(a) 20-50% of an ethylene/propylene elastomeric copolymer containing from 60 to 75% by weight of ethylene, and having a value of Mooney viscosity (ML 1+4) at 100° C. higher than 5;
(b) 0-25% of polypropylene prevailingly constituted by isotactic macromolecules having an M.I. value higher than 1;
(c) 0-70% of substantially amorphous polypropylene, possibly in mixture with amorphous copolymers of ethylene with propylene, such component (c) having a total combined ethylene content lower than 60% by weight, and intrinsic viscosity (in tetralin at 135° C.) lower than 2 dl/g;
(d) 0-25% of polyethylene having density comprised between 0.98 and 0.96 g/cm3, and having a value of M.I. higher than 5;
(e) 0-25% of an ethylene/vinyl acetate (EVA) copolymer containing from 60 to 95% by weight of ethylene, having a value of M.I. higher than 0.1, and with the condition that when component (c) is equal to zero, the component d and the component e are each present in an amount greater than 15% by weight, the sum of components from (a) to (e) being=100.
(2) Bituminous compositions comprising, in mixture, from 10% to 30% by weight, as referred to the total composition weight, of a polymeric composition as defined above.
Description
1. Field of the Invention
The present invention relates to polymeric compositions suitable to be used as agents for bitumen modification, as well as to the so modified bituminous compositions.
2. Description of the Prior Art
The use is known of bituminous compositions, as sheaths, in the water-proofing of civil and industrial buildings. Such compositions are prevailingly constituted by bitumen of the distillate type, and generally contain modifier agents which improve their physical-mechanical characteristics--in particular, their resistance to high-temperature penetration and their low-temperature flexibility. Such agents are generally constituted by amorphous polypropylene (in amount of from 20 to 30% by weight), possibly in combination with amorphous or low-crystallinity olefinic copolymers having low molecular weight.
The Applicant has found now that it is possible to confer to bitumens improved characteristics of low-temperature flexibility and of strength to high-temperature penetration, by using a modifier agent consisting of a polymeric composition comprising, by weight:
(a) 20-50% of an ethylene/propylene elastomeric copolymer containing from 60 to 75% by weight of ethylene, and having a value of Mooney viscosity (ML 1+4) at 100° C. higher than 5 and preferably comprised within the range of from 8 to 40;
(b) 0-25% of polypropylene prevailingly constituted by isotactic macromolecules having M.I. greater than 1 and preferably comprised within the range of from 5 to 15;
(c) 0-70% of substantially amorphous polypropylene, possibly in mixture with amorphous copolymers of ethylene with propylene, such component (c) having a total combined ethylene content lower than 60% by weight, and intrinsic viscosity (in tetralin at 135° C.) lower than 2 dl/g and preferably comprised with the range of from 0.1 to 1;
(d) 0-25% of polyethylene having density comprised between 0.98 and 0.96 g/cm3, and having a value of M.I. higher than 5 and preferably comprised within the range of from 10 to 30;
(e) 0-25% of an ethylene/vinyl acetate (EVA) copolymer containing from 60 to 95% by weight of ethylene, having a value of M.I. higher than 0.1, and preferably comprised within the range of from 0.5 to 200;
with the condition that when component (c) is equal to zero, the component d and the component e are each present in an amount greater than 15% by weight, the sum of components from (a) to (e) being=100.
The polymeric compositions as defined above can be used as modifiers for bitumen by mixing with this latter. Inert mineral fillers, such as silica, kaolin, micas, calcium carbonate etc., can be present in the mixture of bitumen with such modifiers, in amounts of up to 20% by weight as referred to the total mixture weight.
The above said modifier compositions can be used in amounts comprised within the range of from 10 to 30%, but preferably of from 12 to 25% by weight, as referred to the total weight of the mixture with bitumen and possible fillers.
An object of the present invention is hence constituted by the polymeric compositions suitable to be used as additives in bituminous compositions, comprising a mixture of components from (a) to (e) in the above indicated proportions.
A further object of the present invention is constituted by the bituminous compositions comprising from 10% to 30% by weight of the polymeric composition as defined above.
The polymeric compositions of the present invention can be prepared in form of granules by mixing their components either in extruder, or in Banbury or roller mixer, at such temperatures as to allow such components to be intimately mixed in the mixture, and subsequent granulation.
The bituminous compositions which are the further object of the present invention can be prepared by high-temperature mixing bitumen (possibly with the addition of inert mineral fillers such as for example kaolin, CaCO3, SiO2, mica) either with 10-30% by weight, with reference to the total weight of the bituminous composition, of the polymeric composition as defined above, or with the individual components thereof, separately added in an altogether equivalent amount.
The ethylene/propylene copolymers [component (a)] can be prepared according to known methods. Among such copolymers those obtained by using high-yield catalysts, on the basis of titanium comounds, such as, e.g., those disclosed in U.S. Pat. No. 4,013,823 to the Applicant's name, are preferred.
The following Examples are given to the purpose of illustrating the invention without however constituting a limitation thereof.
A bituminous composition is prepared by mixing, in a stainless-steel cylindrical container, at the temperature of 200° C., for 60 minutes and by blade stirrer (500 rpm):
bitumen type 180/200: 65 parts by weight
amorphous polypropylene |η|=0.3: 17 parts by weight
amorphous polypropylenic copolymer containing 50% by weight of ethylene, having |η|=0.3: 5 parts by weight
isotactic polypropylene (Moplen® F30-S from HIMONT Co. (M.I:=12): 3 parts by weight
calcium carbonate: 10 parts by weight
The characteristics of the bituminous composition are reported in Table I.
By operating as in Example 1 a bituminous composition is prepared, which is constituted by:
bitumen type 180/200: 76 parts by weight
ethylene/propylene copolymer, containing 27% of propylene, having Mooney viscosity=11 (ML 1+4 at 100° C.): 6.1 parts by weight
high-density polyethylene (Eraclene® VG 5215 from Enichimica Co.) with M.I.=24.5: 2.4 parts by weight
isotactic polypropylene of Example 1: 3.1 parts by weight
ethylene/vinyl acetate copolymer, containing 15% of vinyl acetate (M.I.=0.6): 2.4 parts by weight
calcium carbonate: 10 parts by weight
The characteristics of the bituminous composition are reported in Table I.
By using a roller mixer a polymeric blend is prepared, which is constituted by the same components as mentioned in Example 2, in the following proportions:
ethylene/propylene copolymer: 44 parts by weight
high-density polyethylene: 17 parts by weight
isotactic polypropylene: 22 parts by weight
ethylene/vinyl acetate copolymer: 17 parts by weight
The so-obtained blend is extruded and granulated.
Eighteen parts by weight of such granulated blend are mixed at 190° C., for 60 minutes and under stirring (500 rpm) with 72 parts by weight of bitumen of the type used in Example 1 and 10 parts by weight of CaCO3.
A bituminous composition, the characteristics of which are reported in Table I, is thus obtained.
TABLE I ______________________________________ 1 (Compar- Examples ative) 2 3 ______________________________________ Penetration at 25° C. dm 46 38 31 (ASTM D5-35) Penetration at 50° C. dm 67 68 48 (ASTM D5-35) Low-temperature Flexibility °C. -10 -13 -15 (UNI 8202) Brookfield Viscosity cps 4000 6000 7000 Elongation at Break, % 20 90 135 Lengthwise (ASTM D412/68) ______________________________________
The bituminous composition is prepared as in Comparative Example 1, with the difference that bitumen of type 80/100 is used.
The characteristics of the mixture are reported in Table II.
In a cylindrical container of 500 cm3 of capacity the following components are blended at 190° C. for 60 minutes under stirring (blade mixer, 500 rpm):
(a) 17 pbw of amorphous polypropylene having |η|=0.3;
(b) 3 pbw of isotactic polypropylene of Example 1;
(c) 5 pbw of an ethylene/propylene copolymer, containing 34% by weight of propylene, and having Mooney viscosity (ML 1+4) at 100° C.=18
(pbw=parts by weight).
Such blend is then added, together with 10 pbw of CaCO3, to 65 pbw of bitumen of type 80:100 to obtain a bituminous composition, by operating as in Example 1.
The characteristics of the so-obtained composition are reported in Table II.
The test of Example 5 is repeated by using an ethylene/propylene copolymer, containing 27% by weight of propylene, having Mooney viscosity (ML 1+4) at 100° C.=34, and adding to bitumen each polymeric component and the filler, separately from each other, thus eliminating the preliminary polymeric blend preparation step.
The characteristics of the bituminous composition so obtained are reported in Table II.
TABLE II ______________________________________ Examples Physical-mechanical charac- 4 teristics of bituminous mixtures (Comparative) 5 6 ______________________________________ Penetration at 25° C. dm 46 43 33 Penetration at 50° C. dm 67 67 63 Low-temperature °C. -6 -9 -6 Flexibility Brookfield Viscosity cps 3500 5000 4000 at 180° C. Elongation at Break, % 20 26 28 Shore A Hardness 61 51 59 ______________________________________
Claims (7)
1. Polymeric compositions suitable for use as bitumen modifiers comprising by weight:
(a) 20-50% b.w. of an ethylene-propylene elastomeric copolymer containing from 60 to 75% b.w. of ethylene and having a value of Mooney viscosity (ML 1+4) at 100° C. higher than 5, said copolymer being prepared by copolymerization of the monomers in the presence of a Ziegler catalyst based on Ti compounds;
(b) 12-25% b.w. of polypropylene prevailingly constituted by isotactic macromolecules having M.I. greater than 1,
(c) a amount greater than 15% and up to 25% b.w. of polyethylene having a density of from 0.96 to 0.98 g/cm3 and having M.I. higher than 5; and
(d) an amount greater than 15% and up to 25% of an ethylene-vinylacetate copolymer containing from 60 to 95% b.w. of ethylene and having M.I. higher than 0.1.
2. Bituminous compositions comprising from 70 to 90% b.w. of bitumen and from 30 to 10% b.w. of a polymeric composition comprising:
(a) 20-50% b.w. to an ethylene-propylene elastomeric copolymer obtained by copolymerization of the monomers in the presence of a Ziegler catalyst based on a titanium compound, said copolymer containing from 60 to 75% b.w. of ethylene and having a Mooney viscosity (ML 1+4) at 100° C. higher than 5;
(b) 12-25% b.w. of polypropylene prevailingly consisting of isotactic macromolecules, having M.I. greater than 1;
(c) an amount greater than 15% and up to 25% b.w. of polyethylene having a density of from 0.96 to 0.98 g/cm3 and M.I. greater than 5; and
(d) an amount greater than 15 and up to 25% b.w. of an ethylene-vinylacetate copolymer containing 60-95% b.w. of ethylene and having M.I. greater than 0.1.
3. Compositions according to claim 1 wherein the component (a) has Mooney Viscosity ML (1+4) at 100° C. comprised between 8 and 40.
4. Composition according to claim 1 or 3 wherein the component (b) has M.I. values comprised between 5 and 15.
5. Compositions according to claim 1 or 3 wherein the component (d) has M.I. values comprised between 10 and 30.
6. Compositions according to claim 1 or 3 wherein the component (e) has M.I. values comprised between 0.5 and 200.
7. Bituminous compositions comprising from 50 to 90% by weight of bitumen, from 0 to 20% by weight of an inert mineral filler and from 10 to 30% by weight of one of polymeric compositions according to claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT20638A/85 | 1985-05-09 | ||
IT20638/85A IT1183590B (en) | 1985-05-09 | 1985-05-09 | POLYMERIC COMPOSITIONS SUITABLE FOR THE MODIFICATION OF THE BITUMU, AND BITUMUNOUS COMPOSITIONS SO MODIFIED |
Publications (1)
Publication Number | Publication Date |
---|---|
US4829109A true US4829109A (en) | 1989-05-09 |
Family
ID=11169888
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/860,917 Expired - Fee Related US4829109A (en) | 1985-05-09 | 1986-05-08 | Polymeric compositions suitable for use as bitumen modifiers and bituminous compositions so modified |
Country Status (5)
Country | Link |
---|---|
US (1) | US4829109A (en) |
EP (1) | EP0204157B1 (en) |
DE (1) | DE3674642D1 (en) |
ES (1) | ES8706764A1 (en) |
IT (1) | IT1183590B (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5068270A (en) * | 1989-07-13 | 1991-11-26 | Nippon Unicar Company Limited | Composition for water proof sheets |
US5077327A (en) * | 1989-08-02 | 1991-12-31 | Himont Incorporated | Spheroidal particulate polymer compositions |
US5093394A (en) * | 1988-09-27 | 1992-03-03 | Sheller-Globe Corporation | Thermoformable acoustical mat composition and method |
US5137947A (en) * | 1989-07-13 | 1992-08-11 | Nippon Unicar Company Ltd. | Composition for water proof sheets |
US5326798A (en) * | 1991-04-15 | 1994-07-05 | Marco Danese | Waterproofing membrane applicable by heating with air-blown bitumen |
US5360849A (en) * | 1992-09-24 | 1994-11-01 | Himont Incorporated | Mixtures of bitumen and polymer compositions suitable for the modification of bitumens |
US5482982A (en) * | 1993-11-22 | 1996-01-09 | Igi Baychem, Inc. | Polymer compositions |
US6284820B1 (en) | 1992-12-28 | 2001-09-04 | Montell Technology Company Bv | Bituminous compositions modified with polyolefinic materials |
US20070054987A1 (en) * | 2005-09-06 | 2007-03-08 | Natalino Zanchetta | Polyethylene modified asphalt compositions |
RU2448994C2 (en) * | 2010-04-19 | 2012-04-27 | Государственное образовательное учреждение высшего профессионального образования "Казанский государственный технологический университет" | Asphalt binder |
EA017056B1 (en) * | 2009-09-15 | 2012-09-28 | Частное Торгово-Производственное Унитарное Предприятие "Новые Административные Технологии" | Polymer modifier for asphaltic concrete and the way of preparation of asphaltic concrete mixture on its basis |
RU2554360C1 (en) * | 2014-04-03 | 2015-06-27 | Святослав Евгеньевич Бурмистров | Bulk additive for asphalt-concrete mixture (versions) and asphalt-concrete mixture |
RU2583016C2 (en) * | 2014-10-01 | 2016-04-27 | Алексей Георгиевич Лысенко | Modifier of organic binder |
RU2615523C1 (en) * | 2015-12-09 | 2017-04-05 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технологический университет" (ФГБОУ ВПО "КНИТУ") | Polymeric bitumen modifier and bitumen-polymer binder based on it |
RU2737926C1 (en) * | 2020-01-16 | 2020-12-04 | федеральное государственное бюджетное образовательное учреждение высшего образования "Алтайский государственный университет" | Method of producing polymer asphalt concrete mixture |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1205998B (en) * | 1987-05-12 | 1989-04-05 | Interchimica Spa | METHOD OF PREPARATION OF A MODIFYER FOR BITUMEN, AND PRODUCT OBTAINED |
IT1217394B (en) * | 1988-04-07 | 1990-03-22 | Ausimont Spa | BITUMEN BASED WATERPROOFING MEMBRANES |
DE3815915A1 (en) * | 1988-05-10 | 1989-11-23 | Ruetgerswerke Ag | SEALING RAIL AND METHOD FOR THEIR PRODUCTION |
JPH075840B2 (en) * | 1989-09-29 | 1995-01-25 | 宇部興産株式会社 | Asphalt composition for waterproof sheet |
ES2049168B1 (en) * | 1992-06-08 | 1994-10-01 | Balram S A | METHOD FOR OBTAINING LAMINABLE PRODUCTS FOR NON-ASPHALT WATERPROOFING AND FOR SOUNDPROOFING AND AS ANTIVIBRATORY, CHLORINE-FREE, AND RESULTING LAMINAR MATERIAL. |
IT1280044B1 (en) * | 1994-02-11 | 1997-12-29 | Enichem Spa | BITUMENS MODIFIED THROUGH POLYMER COMPOSITIONS CONTAINING POLYOLEFINS AND POSSIBLY VIRGIN OR RECYCLED POLYMERS |
EP0718373A1 (en) * | 1994-12-20 | 1996-06-26 | Bridgestone/Firestone, Inc. | Polymer modified asphaltic compounds with improved dispersion and improved products therefrom |
CN102108146B (en) * | 2010-03-29 | 2012-11-21 | 宁波先锋新材料股份有限公司 | Polyolefin thermoplastic elastomer (TPE) composition and preparation method thereof |
CN102585520B (en) * | 2011-12-16 | 2014-02-19 | 陈达溪 | Asphalt modifier suitable for high and cold areas and preparation method and application process thereof |
CN102585521B (en) * | 2011-12-16 | 2014-03-05 | 陈达溪 | Asphalt modifier applicable to hot areas, and preparation method and application process of asphalt modifier |
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- 1986-05-02 DE DE8686106067T patent/DE3674642D1/en not_active Expired - Fee Related
- 1986-05-08 US US06/860,917 patent/US4829109A/en not_active Expired - Fee Related
- 1986-05-08 ES ES555205A patent/ES8706764A1/en not_active Expired
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5093394A (en) * | 1988-09-27 | 1992-03-03 | Sheller-Globe Corporation | Thermoformable acoustical mat composition and method |
US5068270A (en) * | 1989-07-13 | 1991-11-26 | Nippon Unicar Company Limited | Composition for water proof sheets |
US5137947A (en) * | 1989-07-13 | 1992-08-11 | Nippon Unicar Company Ltd. | Composition for water proof sheets |
US5077327A (en) * | 1989-08-02 | 1991-12-31 | Himont Incorporated | Spheroidal particulate polymer compositions |
US5326798A (en) * | 1991-04-15 | 1994-07-05 | Marco Danese | Waterproofing membrane applicable by heating with air-blown bitumen |
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Also Published As
Publication number | Publication date |
---|---|
IT1183590B (en) | 1987-10-22 |
IT8520638A0 (en) | 1985-05-09 |
ES555205A0 (en) | 1987-07-16 |
EP0204157B1 (en) | 1990-10-03 |
DE3674642D1 (en) | 1990-11-08 |
EP0204157A1 (en) | 1986-12-10 |
ES8706764A1 (en) | 1987-07-16 |
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